CN110003751A - A kind of modified graphene oxide/acrylic resin composite anticorrosion coating and its preparation and application - Google Patents
A kind of modified graphene oxide/acrylic resin composite anticorrosion coating and its preparation and application Download PDFInfo
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- CN110003751A CN110003751A CN201910222458.4A CN201910222458A CN110003751A CN 110003751 A CN110003751 A CN 110003751A CN 201910222458 A CN201910222458 A CN 201910222458A CN 110003751 A CN110003751 A CN 110003751A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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Abstract
The invention belongs to the technical field of anticorrosive paint, a kind of modified graphene oxide/acrylic resin composite anticorrosion coating and its preparation and application are disclosed.The modified graphene oxide/acrylic resin composite anticorrosion coating is mainly prepared by following raw material according to parts by weight: modified graphene oxide 0.04~2, hard monomer methyl methacrylate 15~75, soft monomer butyl acrylate 10~45, anti-pollution function monomer 3~10；Wherein modified graphene oxide is obtained by silane coupler modified graphene oxide.The invention also discloses the preparation methods of anticorrosive paint.Coating environmental protection of the invention, has excellent barrier property, cracking phenomena will not occur when thickness applies；And coating of the invention has low-surface-energy, and antifouling effect is good, has preferable Corrosion Protection.The modified graphene oxide/application of the acrylic resin composite anticorrosion coating in Marine Antifouling Paint.
Description
Technical field
The invention belongs to marine anticorrosion corrosion material technical fields, and in particular to a kind of modified graphene oxide/acrylic acid tree
Rouge anticorrosion coating and its preparation and application.
Background technique
Area on the earth there are about 71% is covered by ocean, with going from strength to strength for marine cause, more and more oceans
Engineering armored concrete facility comes into being.Under marine environment, reinforced concrete structure can bear ocean current, sea wind, sea fog, sea
The couplings such as wave, tidal range and marine fouling organism corrosion, enable it that corrosion failure and performance deterioration, clothes occur during service
Use as a servant the lost of life.In addition, the design service life of modern age great reinforced concrete engineering is up to 100 years, and in 100 years, concrete
Surface will form all kinds of fouling communities, physics, the chemistry, biological effect of group's generation after 10~20 years seawater impregnate
Reinforced concrete surface coating " can be nibbled ", reinforcement corrosion is induced, causes concrete cracking.Therefore marine fouling organism is to mixed
The durability of solidifying geotechnique's journey, which influences research, has highly important directive significance.
Marine reinforced concrete structure engineering due to by being destroyed the effects of biology, physics, chemistry in marine environment, how
The corrosion failure process for delaying reinforced concrete works, to bridge, harbour, industrial plants based on armored concrete etc.
It is safely operated most important.Wherein anticorrosion with coat technology is as a kind of simple and easy method, in the guarantor of reinforced concrete works
It is used widely in shield.
Currently, the traditional anticorrosive paint being applied in marine environment is mostly Scale filler type anticorrosive paint, in coating
In overlap distribution, generate labyrinth effect, extend corrosive medium diffusion path.But when filer content is excessively high, coating and matrix
Associativity can be deteriorated, and when film layer is blocked up is also easy to produce cracking, causes coating shield performance poor, in heavily contaminated or harsh marine environment
Middle anti-corrosion life wretched insufficiency.In addition, the effective antifouling paint of tradition is to contain TBT in terms of anti-marine fouling organism attachment
The coating of biocide, however this coating equally has the effect of killing livestock to nontarget organism.And polishing type copper oxide class or oxygen
Changing zinc class antifouling paint becomes the mainstream of the prior art, although meeting current environmental requirement, a large amount of copper, Zn-ef ficiency exist
It is largely gathered in ocean, it is largely dead to will lead to marine growth, destroys the ecological balance.So being badly in need of developing a kind of nontoxic effective
Corrosion-resistant antifouling paint.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, it is an object of that present invention to provide a kind of modified graphene oxide/the third
Olefin(e) acid resin compounded anticorrosive paint.The monomers such as the fluorine of low-surface-energy are introduced into acrylic resin main chain by the present invention, obtain low table
The coating matrix of face energy anti-pollution antibiont attachment, and light modified graphene oxide tough and tensile, that shield effectiveness is excellent is introduced into tree
In rouge, a kind of antifouling corrosion resistant coating of low-surface-energy is finally obtained.
Another object of the present invention is to provide above-mentioned modified graphene oxide/acrylic resin composite anticorrosion coating systems
Preparation Method.
A further object of the present invention is to provide above-mentioned modified graphene oxide/acrylic resin composite anticorrosion coatings to answer
With.The modified graphene oxide/application of the acrylic resin composite anticorrosion coating in Marine Antifouling Paint.
The purpose of the present invention is achieved through the following technical solutions:
A kind of modified graphene oxide/acrylic resin composite anticorrosion coating, mainly by following original according to parts by weight
Material is prepared:
Wherein modified graphene oxide is obtained by silane coupler modified graphene oxide, silane coupling agent and oxidation stone
The mass ratio of black alkene is (1~2): 1.
The anticorrosive paint further includes initiator and solvent；The initiator is azodiisobutyronitrile, the dosage of initiator
It is the 0.5~3% of reactant total weight, reactant is methyl methacrylate, butyl acrylate and anti-pollution function monomer.
The coupling agent contains can be with the group of acrylic, general formula: (RO)2R′Si-(CH2)n- X,
Wherein n=0~3, RO are hydrolysising group, preferably methoxyl group, ethyoxyl, acetoxyl group, propoxyl group, isopropyl oxygen
Base, R ' are methyl, ethyl or hydrolysising group (such as: methoxyl group, ethyoxyl, acetoxyl group, propoxyl group, isopropoxy), and X is organic
Functional group, preferably methacryloxy, vinyl.
The silane coupling agent is preferably 3- methyl allyl acyloxypropyl trimethoxysilane, 3- methacryloxypropyl
Triethoxysilane, 3- methacryloxypropyl methyl dimethoxysilane, 3- methacryloxypropyl methyl dimethoxy oxygen
Base silane, vinyltriethoxysilane, vinyltrimethoxysilane, one of vinyl silane triisopropoxide with
On；
The anti-pollution function monomer is the antifouling factor of monomer with low-surface-energy characteristic, preferably methacrylic acid ten
Difluoro heptyl ester, methacrylic acid hexafluoro isopropyl ester, ten trifluoro monooctyl ester of methacrylic acid, methylvinyl-chlorosilanes or γ-methyl
One or more of acryloyloxypropyltrimethoxysilane.
The solvent be toluene, dimethylbenzene, ethyl acetate, butyl acetate, methylisobutylketone more than one.
The modified graphene oxide is prepared especially by following methods:, will in the ethanol water that pH is 4-5
Silane coupling agent carries out prehydration, and graphene oxide is then added, is uniformly dispersed, and 6~10h is reacted at 70~80 DEG C, cooling,
Washing, obtains modified graphene oxide.
The ethanol water is to mix water with dehydrated alcohol, is then 4-5 acquisition by acid for adjusting pH；Water with it is anhydrous
The volume ratio of ethyl alcohol is 1:(10-20)；The acid is glacial acetic acid.
The condition of the prehydration is prehydration 10-60min at 30-40 DEG C；Described be uniformly dispersed refers to progress ultrasound point
It dissipates, ultrasound 20-60min under the power that ultrasonic condition is 100-1500W.
The modified graphene oxide/acrylic resin composite anticorrosion coating preparation method be one-step method polymerisation in solution or
Two-step method polymerisation in solution；
The one-step method polymerisation in solution refers to: it disperses modified graphene oxide in solvent, part initiator is added,
It is warming up to 70-80 DEG C under inert atmosphere, methyl methacrylate, butyl acrylate, anti-pollution function monomer and residue is added dropwise and draws
Agent is sent out, 3-7h is stirred to react, obtains modified graphene oxide/acrylic acid composite anticorrosion coating.The part initiator is to cause
The 1/4~3/5 of agent total amount；Ultrasound 30-120min under the power that the condition of ultrasound is 100-1500W.The residue initiator can
It is divided into two parts addition, a part is added together with methyl methacrylate, butyl acrylate, anti-pollution function monomer, stirs
1-4h is reacted, last part initiator is then added, is stirred to react 2-3h.
The two-step method polymerisation in solution: dispersing modified graphene oxide in solvent, part initiator is added, in inertia
It is warming up to 70-80 DEG C under atmosphere, methyl methacrylate, butyl acrylate and another part initiator is added dropwise, is stirred to react 2-
4h；Anti-pollution function monomer and remaining initiator is added, it is compound to obtain modified graphene oxide/acrylic acid by the reaction was continued 1-5h
Anticorrosive paint.The part initiator is the 2/5-3/5 of initiator total amount；Another part initiator is initiator total amount
1/5-3/10；Ultrasound 30-120min under the power that the condition of ultrasound is 100-1500W.
The solvent of polymerisation in solution be toluene, dimethylbenzene, ethyl acetate, butyl acetate, methylisobutylketone more than one；Institute
State solvent and reactant (reactant refers to methyl methacrylate, butyl acrylate and anti-pollution function monomer) total mass ratio
For (0.5~2) g:1g；
The initiator is azodiisobutyronitrile, initiator account for reactant (reactant refers to methyl methacrylate, third
Olefin(e) acid butyl ester and anti-pollution function monomer) quality 0.5~3%, time of the dropwise addition is 1.5~3h.
Coating of the invention contains graphene oxide, and graphene oxide is Graphene derivative, it is considered to be most thin corruption
Protection film is lost, due to the big screen effect that its two-dimensional structure has, therefore excellent barrier property can be played；And its is light, has
Machineization is modified can be evenly dispersed in resin, cracking phenomena will not occur when thickness applies.Meanwhile with the low surface of a small amount of valuableness
The good and cheap acrylic resin of the substance modification mechanical property of energy, gained coating not only have excellent mechanical performances and low surface
Energy antifouling properties, while also having both economy.In addition, material of the present invention is one-component material, constructing operation is simply, conveniently.
Prepared anticorrosion material has preferable Corrosion Protection.
Compared with prior art, of the invention to have the following advantages and beneficial effects:
Anticorrosive paint environmental protection of the invention, has excellent barrier property, cracking phenomena will not occur when thickness applies；And
Coating of the invention has low-surface-energy, and antifouling effect is good, has preferable Corrosion Protection.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, but embodiments of the present invention are not limited to
This.
Embodiment 1
The dehydrated alcohol of 5mL deionized water and 60mL are mixed, with the pH value of vinegar acid-conditioning solution to 3~4, are then added
The vinyltriethoxysilane of 0.5g, the prehydration 30min in 30~40 DEG C of water-bath；The graphite oxide of 0.25g is added
Alkene after ultrasonic 1h, is transferred to 80 DEG C of reaction 8h in oil bath pan, discharges, and ethanol water washing is dried to obtain modified graphite oxide
Alkene.
In the four-hole boiling flask with mechanical agitator, reflux condenser, constant pressure separatory funnel and hygrosensor, it is added
73.566g methylisobutylketone, 0.073g modified graphene oxide, ultrasonic disperse 1h；Be passed through nitrogen, be warming up to 70 DEG C, then plus
Enter the azodiisobutyronitrile of 0.736g, stirring and dissolving；Then it is slowly dropped into (time of dropwise addition is 2h) 37.545g methacrylic acid
Methyl esters, 16.021g butyl acrylate, the azodiisobutyronitrile of 20g dodecafluoroheptyl methacrylate and 0.368g, nitrogen protection
Under, it is stirred to react 2 hours, adds 0.368g initiator, continue to be stirred to react 2.5h discharging, obtain modified graphene oxide/the third
Olefin(e) acid resin compounded anticorrosive paint.The coating property test such as table 1 of the present embodiment.
Embodiment 2
The dehydrated alcohol of 5mL deionized water and 60mL are mixed, with the pH value of vinegar acid-conditioning solution to 3~4, are then added
The 3- methacryloxypropyl methyl dimethoxysilane of 0.25g, the prehydration 30min in 30~40 DEG C of water-bath；Add
Enter the graphene oxide of 0.25g, after ultrasonic 1h, be transferred to 80 DEG C of reaction 6h in oil bath pan, discharge, ethanol water washing is dry
Obtain modified graphene oxide.
It is added in the four-hole boiling flask with mechanical agitator, reflux condenser, constant pressure separatory funnel and hygrosensor
57.291g methylisobutylketone, 0.0573g modified graphene oxide, ultrasonic disperse 1h；Nitrogen is then passed to, is warming up to 70 DEG C, so
The azodiisobutyronitrile of 0.573g, stirring and dissolving are added afterwards；Then it is slowly dropped into dissolved with 0.286g azodiisobutyronitrile
37.545g methyl methacrylate, 16.02g butyl acrylate mixed liquor after stirred under nitrogen atmosphere reacts 2 hours, are added
3g3- methyl allyl acyloxypropyl trimethoxysilane and 1.86g dodecafluoroheptyl methacrylate, add 0.286g initiator
Azodiisobutyronitrile continues to be stirred to react 2.5h discharging, obtains modified graphene oxide/acrylic resin composite anticorrosion coating.
The coating property test such as table 1 of the present embodiment.
Embodiment 3
The dehydrated alcohol of 5mL deionized water and 60mL are mixed, with the pH value of vinegar acid-conditioning solution to 3~4, are then added
The 3- methacryloxypropyl methyl dimethoxysilane of 0.25g, the prehydration 30min in 30~40 DEG C of water-bath；Add
Enter the graphene oxide of 0.25g, after ultrasonic 1h, be transferred to 80 DEG C of reaction 6h in oil bath pan, discharge, ethanol water washing is dry
Obtain modified graphene oxide.
It is added in the four-hole boiling flask with mechanical agitator, reflux condenser, constant pressure separatory funnel and hygrosensor
51.36g dimethylbenzene and 5.71g butyl butyrate, 0.0457g modified graphene oxide, ultrasonic disperse 1h.Nitrogen is then passed to, is risen
Then the azodiisobutyronitrile of 0.571g, stirring and dissolving is added to 70 DEG C in temperature；Then it is slowly dropped into different dissolved with 0.285g azo two
The 25.03g methyl methacrylate of butyronitrile, 32.04g butyl acrylate and 8.69g3- methacryloxypropyl trimethoxy
The mixed liquor of silane, stirred under nitrogen atmosphere react 2 hours, add 0.285g initiator azodiisobutyronitrile, and it is anti-to continue stirring
It answers 3h to discharge, obtains modified graphene oxide/acrylic resin composite anticorrosion coating.The coating property test such as table of the present embodiment
1。
The coating property test data of 1 embodiment of table preparation
Comparative example is that (glass-flake coating of DW-YJ type, the good victory in Cangzhou apply common epoxy glass scale coating in table 1
Expect Co., Ltd's production, using epoxy resin as main base, glass flake is filler).
The coating of the coating of Examples 1 to 3 preparation and epoxy glass scale coating is impregnated 90 days in the seawater, this hair
The coating of bright preparation forms coating surface and does not crack, and the coating of epoxy glass scale coating cracks.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (10)
1. a kind of modified graphene oxide/acrylic resin composite anticorrosion coating, it is characterised in that: mainly by it is following by weight
The raw material of number meter is prepared:
Wherein modified graphene oxide is obtained by silane coupler modified graphene oxide.
2. modified graphene oxide/acrylic resin composite anticorrosion coating according to claim 1, it is characterised in that: described
Anti-pollution function monomer is that dodecafluoroheptyl methacrylate, methacrylic acid hexafluoro isopropyl ester, ten trifluoro of methacrylic acid are pungent
One or more of ester, methylvinyl-chlorosilanes or γ-methacryloxypropyl trimethoxy silane；
The general formula of the silane coupling agent: (RO)2R′Si-(CH2)n- X, the wherein integer of n=0~3；RO is hydrolysising group, tool
Body is methoxyl group, ethyoxyl, acetoxyl group, propoxyl group, isopropoxy；R ' be methyl, ethyl or hydrolysising group, hydrolysising group:
Methoxyl group, ethyoxyl, acetoxyl group, propoxyl group, isopropoxy；X is organo-functional group, specially methacryloxypropyl or second
Alkenyl.
3. modified graphene oxide/acrylic resin composite anticorrosion coating according to claim 2, it is characterised in that: described
Silane coupling agent is 3- methyl allyl acyloxypropyl trimethoxysilane, 3- methacryloxypropyl triethoxysilane, 3-
Methacryloxypropyl methyl dimethoxysilane, 3- methacryloxypropyl methyl dimethoxysilane, vinyl three
One or more of Ethoxysilane, vinyltrimethoxysilane or vinyl silane triisopropoxide.
4. modified graphene oxide/acrylic resin composite anticorrosion coating according to claim 1, it is characterised in that:
The mass ratio of the silane coupling agent and graphene oxide is (1~2): 1；
The anticorrosive paint further includes initiator and solvent.
5. modified graphene oxide/acrylic resin composite anticorrosion coating according to claim 4, it is characterised in that: described
Initiator is azodiisobutyronitrile, and the dosage of initiator is the 0.5~3% of reactant total weight, and reactant is methacrylic acid
Methyl esters, butyl acrylate and anti-pollution function monomer；
The solvent is more than one of toluene, dimethylbenzene, ethyl acetate, butyl acetate or methylisobutylketone.
6. modified graphene oxide/acrylic resin composite anticorrosion coating according to claim 1, it is characterised in that: described
Modified graphene oxide is prepared especially by following methods: pH be 4-5 ethanol water in, by silane coupling agent into
Row prehydration, is then added graphene oxide, is uniformly dispersed, and 6~10h is reacted at 70~80 DEG C, cooling, and washing is changed
Property graphene oxide.
7. modified graphene oxide/acrylic resin composite anticorrosion coating according to claim 6, it is characterised in that: described
Ethanol water is to mix water with dehydrated alcohol, is then 4-5 acquisition by acid for adjusting pH；The volume ratio of water and dehydrated alcohol
For 1:(10-20)；
The condition of the prehydration is prehydration 10-60min at 30-40 DEG C.
8. the preparation side of any one modified graphene oxide/acrylic resin composite anticorrosion coating according to claim 1~7
Method, it is characterised in that: be one-step method polymerisation in solution or two-step method polymerisation in solution；
The one-step method polymerisation in solution: dispersing modified graphene oxide in solvent, part initiator is added, in inert atmosphere
Under be warming up to 70-80 DEG C, methyl methacrylate, butyl acrylate, anti-pollution function monomer and remaining initiator, stirring is added dropwise
3-7h is reacted, modified graphene oxide/acrylic acid composite anticorrosion coating is obtained；
The two-step method polymerisation in solution: dispersing modified graphene oxide in solvent, part initiator is added, in inert atmosphere
Under be warming up to 70-80 DEG C, methyl methacrylate, butyl acrylate and another part initiator is added dropwise, is stirred to react 2-4h；Add
Enter anti-pollution function monomer and remaining initiator, the reaction was continued 1-5h obtains modified graphene oxide/acrylic acid composite anti-corrosive and applies
Material.
9. modified graphene oxide/acrylic resin composite anticorrosion coating preparation method according to claim 8, feature
Be: part initiator described in one-step method polymerisation in solution is the 1/4~3/5 of initiator total amount；Ultrasound condition be 100~
30~120min of ultrasound under the power of 1500W；
Part initiator described in two-step method polymerisation in solution is the 2/5~3/5 of initiator total amount；Another part initiator is
The 1/5~3/10 of initiator total amount；30~120min of ultrasound under the power that the condition of ultrasound is 100~1500W；
The solvent and reactant gross mass ratio are (0.5~2) g:1g；The reactant refers to methyl methacrylate, acrylic acid
Butyl ester and anti-pollution function monomer.
10. modified graphene oxide/acrylic resin composite anticorrosion coating is in Marine Antifouling Paint according to claim 8
Application.
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| CN110698941A (en) * | 2019-11-19 | 2020-01-17 | 哈尔滨金士佳科技发展有限公司 | Special heavy-duty anticorrosive paint and preparation method thereof |
| CN111187043A (en) * | 2020-02-24 | 2020-05-22 | 杭州明云混凝土有限公司 | High-strength corrosion-resistant concrete for engineering pile and preparation method thereof |
| CN111303741A (en) * | 2020-03-04 | 2020-06-19 | 绵阳麦思威尔科技有限公司 | High-film-thickness waterborne polyurethane long-acting anticorrosive paint for wind power and petrochemical equipment and preparation method thereof |
| CN111393993A (en) * | 2020-04-24 | 2020-07-10 | 徐金华 | Super-hydrophobic polyaniline-acrylate copolymer anticorrosive coating and preparation method thereof |
| CN112239625A (en) * | 2020-09-25 | 2021-01-19 | 上海大学 | Silicon dioxide-graphene oxide/polyurethane acrylic resin anticorrosion coating |
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| CN115821134A (en) * | 2022-12-01 | 2023-03-21 | 凤阳爱尔思轻合金精密成型有限公司 | Corrosion-resistant aluminum magnesium alloy manufacturing process |
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